WO2022138155A1 - Method for forming insulating film and device for treating insulating film - Google Patents
Method for forming insulating film and device for treating insulating film Download PDFInfo
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- WO2022138155A1 WO2022138155A1 PCT/JP2021/045060 JP2021045060W WO2022138155A1 WO 2022138155 A1 WO2022138155 A1 WO 2022138155A1 JP 2021045060 W JP2021045060 W JP 2021045060W WO 2022138155 A1 WO2022138155 A1 WO 2022138155A1
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- forming
- gas
- insulating film
- substrate
- temperature
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000007789 gas Substances 0.000 claims abstract description 102
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 239000012530 fluid Substances 0.000 claims description 61
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 34
- 229910052581 Si3N4 Inorganic materials 0.000 description 33
- 230000007246 mechanism Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000003028 elevating effect Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/42—Silicides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
Definitions
- This disclosure relates to an insulating film forming method and a processing device.
- a technique of embedding a film from the bottom of a recess from the bottom of the recess by alternately repeating deposition and etching is known (see, for example, Patent Document 1).
- a technique of curing a Si—X film to solidify the film is known (see, for example, Patent Document 2).
- the present disclosure provides a technique capable of embedding a dense nitrogen and / or carbon-containing insulating film in a recess.
- the method for forming an insulating film containing nitrogen and / or carbon is a method for forming an insulating film containing nitrogen and / or carbon in a recess formed on the surface of a substrate (a). ) A step of forming a fluid film in the recess by activating and supplying a processing gas containing a precursor gas and a reducing gas to the substrate adjusted to the first temperature by plasma, and (b) the substrate. It comprises a step of curing the fluid film by heat treatment at a second temperature higher than the first temperature, and the precursor gas is XH x (N z C n H m ) y (X is). It is a Si or a metal element, n, m, x, y are natural numbers of 1 or more, and z is 0 or 1.) It is a linear asymmetric organic molecule having a structure.
- an insulating film containing dense nitrogen and / or carbon can be embedded in the recess.
- Method of forming a silicon nitride film With reference to FIGS. 1 to 4, a method for forming a silicon nitride film will be described as an example of a method for forming an insulating film containing nitrogen and / or carbon. Hereinafter, a method of embedding a silicon nitride film in a recess formed on the surface of a substrate will be described as an example.
- the method for forming a silicon nitride film of the embodiment includes a step S1 for preparing a substrate, a step S2 for forming a fluid film, and a step S3 for curing the fluid film.
- a substrate having a recess formed on the surface is prepared.
- the substrate may be, for example, a semiconductor wafer.
- the recess may be, for example, a trench or a hole.
- the fluid film is formed in the recesses by activating and supplying the processing gas containing the precursor gas and the reducing gas to the substrate adjusted to the first temperature by plasma. ..
- the precursor gas is a linear asymmetric aminosilane molecule having a SiH x (NC n Hm) y (n, m , x, y are natural numbers of 1 or more).
- linear asymmetric aminosilane molecule examples include Vista Shaributylaminosilane (BTBAS), bisdiethylaminosilane (BDEAS), trisdimethylaminosilane (3DMAS), and bisethylmethylaminosilane (BESAS) represented by the following structural formulas.
- the linear asymmetric aminosilane molecule having a SiH x (NC nHm ) y structure has a linear structure and a structure in which the bonds surrounding Si are asymmetric and the dipole moment is large.
- the linear asymmetric aminosilane molecule is electrically activated by plasma and deposited on a substrate regulated to a first temperature.
- the CnHm organic group present at the end of the linear asymmetric aminosilane molecule functions to inhibit the bond with the adjacent molecule and maintain the fluidity. Therefore, since the fluid film is formed so as to flow into the concave portion, it can be embedded in the microstructure. Further, since the C n H m organic group has high stability, the fluidity is maintained even after being embedded in the recess.
- the reducing gas may be a gas containing hydrogen and / or nitrogen, for example, hydrogen (H 2 ) gas, nitrogen (N 2 ) gas, ammonia (NH 3 ) gas, hydrazine (N 2 H 4 ) gas and the like. Combinations and the like can be mentioned.
- the reducing gas is not limited to these.
- the treatment gas may contain an additive gas, and examples of the additive gas include an inert gas such as nitrogen (N 2 ) gas, helium (He), and argon (Ar).
- the first temperature is a temperature at which a fluidized film is formed in the recesses when a processing gas containing a precursor gas and a reducing gas is supplied to the substrate, and may be, for example, 80 ° C. or lower.
- the plasma may be, for example, capacitively coupled plasma, inductively coupled plasma, microwave plasma.
- step S2 for forming the fluid film monosilane (SiH 4 ) gas and disilane (Si 2 H 6 ) gas may be added as the treatment gas. This makes it possible to change the ratio of Si contained in the silicon nitride film embedded in the recess.
- the substrate having the fluid film formed in the recesses is heat-treated at a second temperature higher than the first temperature to cure the fluid film and form a silicon nitride film. ..
- solidification occurs by a condensation reaction between the H group bonded to Si and the amino group between the molecules constituting the fluid film, and a non-porous and dense silicon nitride film is formed.
- the second temperature is a temperature at which the fluidized membrane can be cured, and may be, for example, 150 ° C. or higher and 750 ° C. or lower.
- the step S3 for curing the fluid film is carried out after the step S2 for forming the fluid film without exposing the substrate to the atmosphere. That is, the step S2 for forming the fluid film and the step S3 for curing the fluid film are continuously performed in a vacuum atmosphere.
- the step S3 for curing the fluid film is carried out in a short time (for example, within 60 seconds) after the step S2 for forming the fluid film.
- the fluid film can be solidified by the condensation reaction while the fluid film embedded in the recesses maintains the fluidity. As a result, a non-porous and dense film is formed.
- the substrate it is preferable to expose the substrate to hydrogen plasma.
- the fluid membrane By exposing the substrate to hydrogen plasma, the fluid membrane can be cured while removing impurities contained in the fluid membrane. Therefore, the concentration of impurities in the silicon nitride film embedded in the recess can be reduced.
- the hydrogen plasma may be, for example, a plasma using a VHF wave of 100 MHz to 1 GHz.
- processing apparatus membrane forming portion
- the processing device heat treatment unit
- the processing device that carries out the step S3 for curing the fluid film may have the same configuration as the processing device that carries out the step S2 for forming the fluid film.
- the processing apparatus 1 uses a plasma-based chemical vapor deposition (CVD) method to silicon nitride a semiconductor wafer (hereinafter referred to as “wafer W”), which is an example of a substrate. It is a device that forms a film.
- the processing device 1 includes a substantially cylindrical airtight processing container 2.
- An exhaust chamber 21 is provided in the central portion of the bottom wall of the processing container 2.
- the exhaust chamber 21 has, for example, a substantially cylindrical shape that protrudes downward.
- An exhaust flow path 22 is connected to the exhaust chamber 21, for example, on the side surface of the exhaust chamber 21.
- the exhaust section 24 is connected to the exhaust flow path 22 via the pressure adjusting section 23.
- the pressure adjusting unit 23 includes a pressure adjusting valve such as a butterfly valve.
- the exhaust flow path 22 is configured so that the inside of the processing container 2 can be depressurized by the exhaust unit 24.
- a transport port 25 is provided on the side surface of the processing container 2.
- the transport port 25 is configured to be openable and closable by a gate valve 26. The loading and unloading of the wafer W between the inside of the processing container 2 and the transport chamber (not shown) is performed via the transport port 25.
- a mounting table 3 for holding the wafer W substantially horizontally is provided in the processing container 2.
- the mounting table 3 is formed in a substantially circular shape in a plan view, and is supported by a support member 31.
- the recess 32 has an inner diameter slightly larger than the diameter of the wafer W (for example, about 1 mm to 4 mm).
- the depth of the recess 32 is configured to be substantially the same as the thickness of the wafer W, for example.
- the mounting table 3 is made of a ceramic material such as aluminum nitride (AlN). Further, the mounting table 3 may be formed of a metal material such as nickel (Ni).
- a guide ring for guiding the wafer W may be provided on the peripheral edge of the surface of the mounting table 3.
- a grounded lower electrode 33 is embedded in the mounting table 3.
- a temperature control mechanism 34 is embedded below the lower electrode 33.
- the temperature control mechanism 34 sets the wafer W mounted on the mounting table 3 at a set temperature (for example, a temperature of ⁇ 50 ° C. to 80 ° C., and for a mounting table for heat treatment, for example, 150 ° C., based on a control signal from the control unit 9. Adjust to a temperature of ⁇ 750 ° C.).
- the entire mounting table 3 is made of metal, the entire mounting table 3 functions as a lower electrode, so that the lower electrode 33 does not have to be embedded in the mounting table 3.
- the mounting table 3 is provided with a plurality of (for example, three) lifting pins 41 for holding and raising and lowering the wafer W mounted on the mounting table 3.
- the material of the elevating pin 41 may be, for example, ceramics such as alumina (Al 2 O 3 ), quartz, or the like.
- the lower end of the elevating pin 41 is attached to the support plate 42.
- the support plate 42 is connected to an elevating mechanism 44 provided outside the processing container 2 via an elevating shaft 43.
- the elevating mechanism 44 is installed, for example, at the lower part of the exhaust chamber 21.
- the bellows 45 is provided between the opening 211 for the elevating shaft 43 formed on the lower surface of the exhaust chamber 21 and the elevating mechanism 44.
- the shape of the support plate 42 may be a shape that can be raised and lowered without interfering with the support member 31 of the mounting table 3.
- the elevating pin 41 is vertically configured by the elevating mechanism 44 between the upper side of the surface of the mounting table 3 and the lower side of the surface of the mounting table 3. In other words, the elevating pin 41 is configured to be able to project from the upper surface of the mounting table 3.
- the top wall 27 of the processing container 2 is provided with a gas supply unit 5 via an insulating member 28.
- the gas supply unit 5 forms an upper electrode and faces the lower electrode 33.
- An RF power supply 51 is connected to the gas supply unit 5 via a matching unit 511.
- the frequency of the RF power supply 51 is, for example, 450 kHz to 2.45 GHz.
- the gas supply unit 5 includes a hollow gas diffusion chamber 52. On the lower surface of the gas diffusion chamber 52, for example, a large number of holes 53 for dispersing and supplying the processing gas into the processing container 2 are evenly arranged.
- a heating mechanism 54 is embedded above, for example, the gas diffusion chamber 52 in the gas supply unit 5.
- the heating mechanism 54 is heated to a set temperature by supplying power from a power supply unit (not shown) based on a control signal from the control unit 9.
- the gas diffusion chamber 52 is provided with a gas supply path 6.
- the gas supply path 6 communicates with the gas diffusion chamber 52.
- a gas source 61 is connected to the upstream side of the gas supply path 6 via a gas line 62.
- the gas source 61 includes, for example, various processing gas supply sources, a mass flow controller, and valves (none of which are shown).
- the various treatment gases include a precursor gas and a reducing gas used in the above-mentioned method for forming a silicon nitride film. Further, the various treatment gases may contain an additive gas such as a monosilane gas or a disilane gas.
- Various treated gases are introduced from the gas source 61 into the gas diffusion chamber 52 via the gas line 62.
- the processing device 1 includes a control unit 9.
- the control unit 9 is, for example, a computer, and includes a CPU (Central Processing Unit), a RAM (RandomAccessMemory), a ROM (ReadOnlyMemory), an auxiliary storage device, and the like.
- the CPU operates based on a program stored in the ROM or the auxiliary storage device, and controls the operation of the processing device 1.
- the control unit 9 may be provided inside the processing device 1 or may be provided outside. When the control unit 9 is provided outside the processing device 1, the control unit 9 can control the processing device 1 by a communication means such as wired or wireless.
- Example 1 a wafer W having a concave portion having an aspect ratio smaller than 1 formed on the surface was prepared. Subsequently, in the processing apparatus 1, with the wafer W mounted on the mounting table 3, the processing gas containing the precursor gas and the reducing gas is supplied from the gas supply unit 5 into the processing container 2, and the RF power source 51 is used. RF power was supplied from the upper electrode to the wafer W to form a fluid film. Subsequently, the wafer W on which the fluidized film was formed was conveyed to another processing apparatus 1 in a vacuum atmosphere. Subsequently, in the processing apparatus 1, the wafer W is heat-treated at 450 ° C.
- the film forming conditions of the fluid film in Example 1 are as follows. -Precursor gas: BTBAS (50 sccm) -Reducing gas: NH 3 (50 sccm) -Additional gas: H 2 (50 sccm), He (50 sccm) -Pressure: 4Torr (533Pa) ⁇ RF power: 13.56MHz, 100W ⁇ Wafer temperature: 0 ° C
- Example 2 a wafer W having a concave portion having an aspect ratio larger than 5 formed on the surface is prepared, a fluid film is formed on the wafer W under the same conditions as in Example 1, and then the fluid film is cured. A silicon nitride film was formed. Subsequently, the embedding property of the silicon nitride film embedded in the recess was observed by SEM.
- Comparative Example 1 the time from the completion of the formation of the fluidized film on the wafer W to the start of the heat treatment for the fluidized film is set to 1 hour, and other conditions are the same as in Example 1. Under the conditions, a fluidized film was formed on the wafer W, and then the fluidized film was cured to form a silicon nitride film. Subsequently, the embedding property of the silicon nitride film embedded in the recess was observed by SEM. In Comparative Example 1, a wafer W having a recess formed on the surface having an aspect ratio larger than 5 was used.
- TeDMAS tetrakisdimethylaminosilane
- FIG. 6 is a diagram showing the results of observing the embedding property of the silicon nitride film embedded in the recess, and shows the cross-sectional shape of the silicon nitride film embedded in the recess. Note that FIG. 6 shows the results of Example 1, Example 2, Comparative Example 1 and Comparative Example 2 in order from the left.
- a non-porous and dense silicon nitride film 101 having no voids (gap) or seams (seam) is embedded in the vicinity of the bottom of the recess.
- the fluid film formed in the recess is heat-treated in a state where the fluidity is maintained, and during the heat treatment, the fluid film is solidified by a condensation reaction to form a silicon nitride film. It is thought that it was a heat treatment.
- Comparative Example 1 it can be seen that the porous silicon nitride film 102 including a large number of pores 102a is embedded in the vicinity of the bottom of the recess. It is considered that this is because, in Comparative Example 1, the fluid film formed in the recess was heat-treated in a state where the fluidity was lost, and the film deposition was reduced during the heat treatment to form a porous structure.
- Comparative Example 2 it can be seen that the silicon nitride film is not embedded in the recess. This is because in Comparative Example 2, by using an aminosilane molecule having a symmetrical structure that does not have a Si—H bond as the precursor gas, the condensation reaction of the fluid film formed in the recesses even after the heat treatment was performed. It is probable that the solidification did not proceed and the fluid membrane disappeared.
- a silicon nitride film is formed by using a linear asymmetric aminosilane molecule having a SiH x (NC n Hm) y (n, m , x, y are natural numbers of 1 or more) structure as a precursor gas.
- NC n Hm SiH x
- y n, m , x, y are natural numbers of 1 or more structure
- the present disclosure is not limited to this.
- an MH x (NC n Hm) y ( M is a metal element
- n, m, x, y are natural numbers of 1 or more) containing a metal element instead of Si as a precursor gas. It can also be applied when forming a metal nitride film using linear asymmetric organic metal molecules.
- a linear asymmetric organic molecule having an XH x (NC n Hm) y (X is Si or a metal element, and n, m , x, y are natural numbers of 1 or more) as a precursor gas. It can be applied when forming a nitrogen-containing film.
- the metal element include titanium (Ti), tantalum (Ta), zirconium (Zr), and aluminum (Al).
- the treatment gas contains a precursor gas and a reducing gas and the precursor gas is a linear asymmetric aminosilane molecule
- the present disclosure is not limited thereto.
- a linear asymmetric organic Si molecule having a structure in which the bond surrounding Si is asymmetric and the dipole moment is large may be used.
- the formation of a SiC film can be mentioned as a fluid carbon-containing insulating film using an asymmetric organic Si molecule having a SiH x (C nH m ) y ( n , m, x, y are natural numbers of 1 or more).
- an asymmetric organic metal molecule having an MH x (C n H m ) y (M is a metal element, and n, m, x, y are natural numbers of 1 or more) is used. It can also be applied when forming a metal carbide film. That is, as the precursor gas, XH x (N z C n H m ) y (X is Si or a metal element, n, m, x, y are natural numbers of 1 or more, and z is 0 or 1. ) Applicable when forming an insulating film containing nitrogen and / or carbon using linear asymmetric organic molecules of structure.
- the step of forming the fluid film and the step of curing the fluid film are carried out in different processing devices connected to the vacuum transfer device, but the present disclosure is not limited to this.
- the step of forming the fluid film and the step of curing the fluid film may be carried out in the same processing apparatus.
- a processing apparatus having a first region for heating the substrate to the first temperature for processing and a second region for heating the substrate to the second temperature for processing may be used.
- the step of forming the fluid film and the step of curing the fluid film can be performed in different regions in one processing apparatus, the fluid film is cured after the step of forming the fluid film is completed.
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Abstract
The method for forming an insulating film containing nitrogen and/or carbon according to one mode of the present disclosure is a method for forming an insulating film containing nitrogen and/or carbon in a recessed portion formed in the surface of a substrate. The method comprises: (a) a step for forming a fluidic film in the recessed portion by feeding, to the substrate adjusted to a first temperature, a treatment gas containing a precursor gas and a reducing gas and by activating the treatment gas with plasma, and (b) a step for curing the fluidic film by a heating the substrate at a second temperature higher than the first temperature. The precursor gas is a linear non-symmetric organic molecule having an XHx(NzCnHm)y structure (X represents Si or a metal element, n, m, x, and y represent a natural number of at least 1, and z represents 0 or 1).
Description
本開示は、絶縁膜の形成方法及び処理装置に関する。
This disclosure relates to an insulating film forming method and a processing device.
半導体製造プロセスにおいて、構造の微細化に伴いアスペクト比が高い凹部にボイドやシームなく膜を埋め込むことが求められている。
In the semiconductor manufacturing process, it is required to embed a film in a recess having a high aspect ratio without voids or seams as the structure becomes finer.
埋め込みプロセスの一例としては、堆積とエッチングとを交互に繰り返すことで凹部の底部からボトムアップで膜を埋め込む技術が知られている(例えば、特許文献1参照)。埋込プロセスの別の一例としては、PECVDによって流動性膜を形成し、該流動性膜を処理してSi-X膜を形成し(X=C、O、又はNである)、流動性膜又はSi-X膜を硬化して膜を固化させる技術が知られている(例えば、特許文献2参照)。
As an example of the embedding process, a technique of embedding a film from the bottom of a recess from the bottom of the recess by alternately repeating deposition and etching is known (see, for example, Patent Document 1). As another example of the embedding process, a fluid film is formed by PECVD, the fluid film is treated to form a Si—X film (X = C, O, or N), and the fluid film is formed. Alternatively, a technique of curing a Si—X film to solidify the film is known (see, for example, Patent Document 2).
本開示は、緻密な窒素及び/又は炭素を含有する絶縁膜を凹部に埋め込むことができる技術を提供する。
The present disclosure provides a technique capable of embedding a dense nitrogen and / or carbon-containing insulating film in a recess.
本開示の一態様による窒素及び/又は炭素を含有する絶縁膜の形成方法は、基板の表面に形成された凹部に窒素及び/又は炭素を含有する絶縁膜を形成する方法であって、(a)第1の温度に調整された基板に前駆体ガス及び還元性ガスを含む処理ガスをプラズマで活性化して供給することにより前記凹部に流動性膜を形成する工程と、(b)前記基板を前記第1の温度より高い第2の温度で熱処理することにより前記流動性膜を硬化させる工程と、を有し、前記前駆体ガスは、XHx(NzCnHm)y(XはSi又は金属元素であり、n、m、x、yは1以上の自然数であり、zは0または1である。)構造の線形非対称有機分子である。
The method for forming an insulating film containing nitrogen and / or carbon according to one aspect of the present disclosure is a method for forming an insulating film containing nitrogen and / or carbon in a recess formed on the surface of a substrate (a). ) A step of forming a fluid film in the recess by activating and supplying a processing gas containing a precursor gas and a reducing gas to the substrate adjusted to the first temperature by plasma, and (b) the substrate. It comprises a step of curing the fluid film by heat treatment at a second temperature higher than the first temperature, and the precursor gas is XH x (N z C n H m ) y (X is). It is a Si or a metal element, n, m, x, y are natural numbers of 1 or more, and z is 0 or 1.) It is a linear asymmetric organic molecule having a structure.
本開示によれば、緻密な窒素及び/又は炭素を含有する絶縁膜を凹部に埋め込むことができる。
According to the present disclosure, an insulating film containing dense nitrogen and / or carbon can be embedded in the recess.
以下、添付の図面を参照しながら、本開示の限定的でない例示の実施形態について説明する。添付の全図面中、同一又は対応する部材又は部品については、同一又は対応する参照符号を付し、重複する説明を省略する。
Hereinafter, non-limiting exemplary embodiments of the present disclosure will be described with reference to the accompanying drawings. In all the attached drawings, the same or corresponding members or parts are designated by the same or corresponding reference numerals, and duplicate description is omitted.
〔シリコン窒化膜の形成方法〕
図1~図4を参照し、窒素及び/又は炭素を含有する絶縁膜を形成する方法の一例として、シリコン窒化膜の形成方法について説明する。以下では、基板の表面に形成された凹部にシリコン窒化膜を埋め込む方法を例に挙げて説明する。 [Method of forming a silicon nitride film]
With reference to FIGS. 1 to 4, a method for forming a silicon nitride film will be described as an example of a method for forming an insulating film containing nitrogen and / or carbon. Hereinafter, a method of embedding a silicon nitride film in a recess formed on the surface of a substrate will be described as an example.
図1~図4を参照し、窒素及び/又は炭素を含有する絶縁膜を形成する方法の一例として、シリコン窒化膜の形成方法について説明する。以下では、基板の表面に形成された凹部にシリコン窒化膜を埋め込む方法を例に挙げて説明する。 [Method of forming a silicon nitride film]
With reference to FIGS. 1 to 4, a method for forming a silicon nitride film will be described as an example of a method for forming an insulating film containing nitrogen and / or carbon. Hereinafter, a method of embedding a silicon nitride film in a recess formed on the surface of a substrate will be described as an example.
図1に示されるように、実施形態のシリコン窒化膜の形成方法は、基板を準備する工程S1と、流動性膜を形成する工程S2と、流動性膜を硬化させる工程S3とを有する。
As shown in FIG. 1, the method for forming a silicon nitride film of the embodiment includes a step S1 for preparing a substrate, a step S2 for forming a fluid film, and a step S3 for curing the fluid film.
基板を準備する工程S1では、表面に凹部が形成された基板を準備する。基板は、例えば半導体ウエハであってよい。凹部は、例えばトレンチ、ホールであってよい。
In the step S1 of preparing the substrate, a substrate having a recess formed on the surface is prepared. The substrate may be, for example, a semiconductor wafer. The recess may be, for example, a trench or a hole.
流動性膜を形成する工程S2では、第1の温度に調整された基板に前駆体ガス及び還元性ガスを含む処理ガスをプラズマで活性化して供給することにより、凹部に流動性膜を形成する。
In the step S2 for forming the fluid film, the fluid film is formed in the recesses by activating and supplying the processing gas containing the precursor gas and the reducing gas to the substrate adjusted to the first temperature by plasma. ..
本実施形態において、前駆体ガスは、SiHx(NCnHm)y(n、m、x、yは1以上の自然数である。)構造の線形非対称アミノシラン分子である。線形非対称アミノシラン分子としては、例えば以下の構造式で示されるビスターシャリブチルアミノシラン(BTBAS)、ビスジエチルアミノシラン(BDEAS)、トリスジメチルアミノシラン(3DMAS)、ビスエチルメチルアミノシラン(BEMAS)が挙げられる。
In the present embodiment, the precursor gas is a linear asymmetric aminosilane molecule having a SiH x (NC n Hm) y (n, m , x, y are natural numbers of 1 or more). Examples of the linear asymmetric aminosilane molecule include Vista Shaributylaminosilane (BTBAS), bisdiethylaminosilane (BDEAS), trisdimethylaminosilane (3DMAS), and bisethylmethylaminosilane (BESAS) represented by the following structural formulas.
SiHx(NCnHm)y構造の線形非対称アミノシラン分子は、直鎖構造であり、かつ、Siを取り巻く結合が非対称であり双極子モーメントが大きくなる構造である。係る線形非対称アミノシラン分子をプラズマで電気的に活性化させ、第1の温度に調整された基板に堆積させる。このとき、線形非対称アミノシラン分子の末端に存在するCnHm有機基は、隣接する分子との結合を阻害して流動性を維持するように機能する。そのため、凹部に流れ込むようにして流動性膜が形成されるので、微細構造への埋め込みが可能となる。また、CnHm有機基は安定性が高いため、凹部に埋め込まれた後も流動性が維持される。
The linear asymmetric aminosilane molecule having a SiH x (NC nHm ) y structure has a linear structure and a structure in which the bonds surrounding Si are asymmetric and the dipole moment is large. The linear asymmetric aminosilane molecule is electrically activated by plasma and deposited on a substrate regulated to a first temperature. At this time, the CnHm organic group present at the end of the linear asymmetric aminosilane molecule functions to inhibit the bond with the adjacent molecule and maintain the fluidity. Therefore, since the fluid film is formed so as to flow into the concave portion, it can be embedded in the microstructure. Further, since the C n H m organic group has high stability, the fluidity is maintained even after being embedded in the recess.
例えば、前駆体ガスとしてBTBASを用いた場合、図2に示されるように、隣接するBTBAS分子間においてプラズマ重合が生じ、次いで図3に示されるように、プラズマ重合で生じた分子間において更にプラズマ重合が生じ、オリゴマーが生成される。
For example, when BTBAS is used as the precursor gas, plasma polymerization occurs between adjacent BTBAS molecules as shown in FIG. 2, and then further plasma occurs between the molecules generated by plasma polymerization as shown in FIG. Polymerization occurs and oligomers are produced.
還元性ガスは、水素及び/又は窒素を含むガスであってよく、例えば水素(H2)ガス、窒素(N2)ガス、アンモニア(NH3)ガス、ヒドラジン(N2H4)ガス及びその組合せ等が挙げられる。なお、還元ガスはこれらに限るものではない。また、処理ガスは、添加ガスを含んでもよい、添加ガスは、例えば窒素(N2)ガス、ヘリウム(He)、アルゴン(Ar)等の不活性ガスを挙げることができる。
The reducing gas may be a gas containing hydrogen and / or nitrogen, for example, hydrogen (H 2 ) gas, nitrogen (N 2 ) gas, ammonia (NH 3 ) gas, hydrazine (N 2 H 4 ) gas and the like. Combinations and the like can be mentioned. The reducing gas is not limited to these. Further, the treatment gas may contain an additive gas, and examples of the additive gas include an inert gas such as nitrogen (N 2 ) gas, helium (He), and argon (Ar).
第1の温度は、基板に前駆体ガス及び還元性ガスを含む処理ガスを供給したときに凹部に流動性膜が形成される温度であり、例えば80℃以下であってよい。プラズマは、例えば容量結合プラズマ、誘導結合プラズマ、マイクロ波プラズマであってよい。
The first temperature is a temperature at which a fluidized film is formed in the recesses when a processing gas containing a precursor gas and a reducing gas is supplied to the substrate, and may be, for example, 80 ° C. or lower. The plasma may be, for example, capacitively coupled plasma, inductively coupled plasma, microwave plasma.
また、流動性膜を形成する工程S2では、処理ガスとして、モノシラン(SiH4)ガス、ジシラン(Si2H6)ガスを添加してもよい。これにより、凹部に埋め込まれるシリコン窒化膜に含まれるSiの比率を変えることができる。
Further, in the step S2 for forming the fluid film, monosilane (SiH 4 ) gas and disilane (Si 2 H 6 ) gas may be added as the treatment gas. This makes it possible to change the ratio of Si contained in the silicon nitride film embedded in the recess.
流動性膜を硬化させる工程S3では、凹部に流動性膜が形成された基板を、第1の温度より高い第2の温度で熱処理することにより流動性膜を硬化させ、シリコン窒化膜を形成する。このとき、流動性膜を構成する分子間において、Siと結合したH基とアミノ基との間で縮合反応による固化が起こり、無孔質で緻密なシリコン窒化膜が形成される。
In the step S3 of curing the fluid film, the substrate having the fluid film formed in the recesses is heat-treated at a second temperature higher than the first temperature to cure the fluid film and form a silicon nitride film. .. At this time, solidification occurs by a condensation reaction between the H group bonded to Si and the amino group between the molecules constituting the fluid film, and a non-porous and dense silicon nitride film is formed.
例えば、前駆体ガスとしてBTBASを用いた場合、図4に示されるように、隣接するオリゴマー間において縮合反応が生じ、流動性膜が硬化してシリコン窒化膜が形成される。
For example, when BTBAS is used as the precursor gas, as shown in FIG. 4, a condensation reaction occurs between adjacent oligomers, the fluid film is cured, and a silicon nitride film is formed.
第2の温度は、流動性膜を硬化させることができる温度であり、例えば150℃以上750℃以下であってよい。
The second temperature is a temperature at which the fluidized membrane can be cured, and may be, for example, 150 ° C. or higher and 750 ° C. or lower.
本実施形態において、流動性膜を硬化させる工程S3は、流動性膜を形成する工程S2の後に、基板を大気に晒すことなく実施される。すなわち、流動性膜を形成する工程S2及び流動性膜を硬化させる工程S3は、真空雰囲気下で連続して実施される。
In the present embodiment, the step S3 for curing the fluid film is carried out after the step S2 for forming the fluid film without exposing the substrate to the atmosphere. That is, the step S2 for forming the fluid film and the step S3 for curing the fluid film are continuously performed in a vacuum atmosphere.
また、流動性膜を硬化させる工程S3は、流動性膜を形成する工程S2の後、短時間(例えば、60秒以内)で実施することが好ましい。これにより、流動性膜を形成する工程S2において凹部に埋め込まれた流動性膜が流動性を維持した状態で、流動性膜を縮合反応で固化させることができる。その結果、無孔質で緻密な膜が形成される。
Further, it is preferable that the step S3 for curing the fluid film is carried out in a short time (for example, within 60 seconds) after the step S2 for forming the fluid film. Thereby, in the step S2 for forming the fluid film, the fluid film can be solidified by the condensation reaction while the fluid film embedded in the recesses maintains the fluidity. As a result, a non-porous and dense film is formed.
また、流動性膜を硬化させる工程S3では、基板を水素プラズマに晒すことが好ましい。基板を水素プラズマに晒すことで、流動性膜に含まれる不純物を除去しながら流動性膜を硬化させることができる。そのため、凹部に埋め込まれるシリコン窒化膜の膜中不純物濃度を低減できる。水素プラズマは、例えば100MHz~1GHzのVHF波を用いるプラズマであってよい。
Further, in the step S3 of curing the fluid film, it is preferable to expose the substrate to hydrogen plasma. By exposing the substrate to hydrogen plasma, the fluid membrane can be cured while removing impurities contained in the fluid membrane. Therefore, the concentration of impurities in the silicon nitride film embedded in the recess can be reduced. The hydrogen plasma may be, for example, a plasma using a VHF wave of 100 MHz to 1 GHz.
〔処理装置〕
図5を参照し、前述した流動性膜を形成する工程S2を実施する処理装置(膜形成部)の一例について説明する。なお、流動性膜を硬化させる工程S3を実施する処理装置(熱処理部)についても流動性膜を形成する工程S2を実施する処理装置と同様の構成であってよい。 [Processing equipment]
With reference to FIG. 5, an example of a processing apparatus (membrane forming portion) for carrying out the above-mentioned step S2 for forming a fluid film will be described. The processing device (heat treatment unit) that carries out the step S3 for curing the fluid film may have the same configuration as the processing device that carries out the step S2 for forming the fluid film.
図5を参照し、前述した流動性膜を形成する工程S2を実施する処理装置(膜形成部)の一例について説明する。なお、流動性膜を硬化させる工程S3を実施する処理装置(熱処理部)についても流動性膜を形成する工程S2を実施する処理装置と同様の構成であってよい。 [Processing equipment]
With reference to FIG. 5, an example of a processing apparatus (membrane forming portion) for carrying out the above-mentioned step S2 for forming a fluid film will be described. The processing device (heat treatment unit) that carries out the step S3 for curing the fluid film may have the same configuration as the processing device that carries out the step S2 for forming the fluid film.
図5に示されるように、処理装置1は、プラズマを用いた化学気相堆積(CVD:Chemical Vapor Deposition)法により、基板の一例である半導体ウエハ(以下「ウエハW」という。)にシリコン窒化膜を形成する装置である。処理装置1は、略円筒状の気密な処理容器2を備える。処理容器2の底壁の中央部分には、排気室21が設けられている。
As shown in FIG. 5, the processing apparatus 1 uses a plasma-based chemical vapor deposition (CVD) method to silicon nitride a semiconductor wafer (hereinafter referred to as “wafer W”), which is an example of a substrate. It is a device that forms a film. The processing device 1 includes a substantially cylindrical airtight processing container 2. An exhaust chamber 21 is provided in the central portion of the bottom wall of the processing container 2.
排気室21は、下方に向けて突出する例えば略円筒状の形状を備える。排気室21には、例えば排気室21の側面において、排気流路22が接続されている。
The exhaust chamber 21 has, for example, a substantially cylindrical shape that protrudes downward. An exhaust flow path 22 is connected to the exhaust chamber 21, for example, on the side surface of the exhaust chamber 21.
排気流路22には、圧力調整部23を介して排気部24が接続されている。圧力調整部23は、例えばバタフライバルブ等の圧力調整バルブを備える。排気流路22は、排気部24によって処理容器2内を減圧できるように構成されている。処理容器2の側面には、搬送口25が設けられている。搬送口25は、ゲートバルブ26によって開閉自在に構成されている。処理容器2内と搬送室(図示せず)との間におけるウエハWの搬入出は、搬送口25を介して行われる。
The exhaust section 24 is connected to the exhaust flow path 22 via the pressure adjusting section 23. The pressure adjusting unit 23 includes a pressure adjusting valve such as a butterfly valve. The exhaust flow path 22 is configured so that the inside of the processing container 2 can be depressurized by the exhaust unit 24. A transport port 25 is provided on the side surface of the processing container 2. The transport port 25 is configured to be openable and closable by a gate valve 26. The loading and unloading of the wafer W between the inside of the processing container 2 and the transport chamber (not shown) is performed via the transport port 25.
処理容器2内には、ウエハWを略水平に保持するための載置台3が設けられている。載置台3は、平面視で略円形状に形成されており、支持部材31によって支持されている。載置台3の表面には、例えば直径が300mmのウエハWを載置するための略円形状の凹部32が形成されている。凹部32は、ウエハWの直径よりも僅かに(例えば1mm~4mm程度)大きい内径を有する。凹部32の深さは、例えばウエハWの厚さと略同一に構成される。載置台3は、例えば窒化アルミニウム(AlN)等のセラミックス材料により形成されている。また、載置台3は、ニッケル(Ni)等の金属材料により形成されていてもよい。なお、凹部32の代わりに載置台3の表面の周縁部にウエハWをガイドするガイドリングを設けてもよい。
A mounting table 3 for holding the wafer W substantially horizontally is provided in the processing container 2. The mounting table 3 is formed in a substantially circular shape in a plan view, and is supported by a support member 31. On the surface of the mounting table 3, for example, a substantially circular recess 32 for mounting a wafer W having a diameter of 300 mm is formed. The recess 32 has an inner diameter slightly larger than the diameter of the wafer W (for example, about 1 mm to 4 mm). The depth of the recess 32 is configured to be substantially the same as the thickness of the wafer W, for example. The mounting table 3 is made of a ceramic material such as aluminum nitride (AlN). Further, the mounting table 3 may be formed of a metal material such as nickel (Ni). Instead of the recess 32, a guide ring for guiding the wafer W may be provided on the peripheral edge of the surface of the mounting table 3.
載置台3には、例えば接地された下部電極33が埋設される。下部電極33の下方には、温調機構34が埋設される。温調機構34は、制御部9からの制御信号に基づいて、載置台3に載置されたウエハWを設定温度(例えば-50℃~80℃の温度、熱処理用の載置台では例えば150℃~750℃の温度)に調整する。載置台3の全体が金属によって構成されている場合には、載置台3の全体が下部電極として機能するので、下部電極33を載置台3に埋設しなくてよい。載置台3には、載置台3に載置されたウエハWを保持して昇降するための複数本(例えば3本)の昇降ピン41が設けられている。昇降ピン41の材料は、例えばアルミナ(Al2O3)等のセラミックスや石英等であってよい。昇降ピン41の下端は、支持板42に取り付けられている。支持板42は、昇降軸43を介して処理容器2の外部に設けられた昇降機構44に接続されている。
For example, a grounded lower electrode 33 is embedded in the mounting table 3. A temperature control mechanism 34 is embedded below the lower electrode 33. The temperature control mechanism 34 sets the wafer W mounted on the mounting table 3 at a set temperature (for example, a temperature of −50 ° C. to 80 ° C., and for a mounting table for heat treatment, for example, 150 ° C., based on a control signal from the control unit 9. Adjust to a temperature of ~ 750 ° C.). When the entire mounting table 3 is made of metal, the entire mounting table 3 functions as a lower electrode, so that the lower electrode 33 does not have to be embedded in the mounting table 3. The mounting table 3 is provided with a plurality of (for example, three) lifting pins 41 for holding and raising and lowering the wafer W mounted on the mounting table 3. The material of the elevating pin 41 may be, for example, ceramics such as alumina (Al 2 O 3 ), quartz, or the like. The lower end of the elevating pin 41 is attached to the support plate 42. The support plate 42 is connected to an elevating mechanism 44 provided outside the processing container 2 via an elevating shaft 43.
昇降機構44は、例えば排気室21の下部に設置されている。ベローズ45は、排気室21の下面に形成された昇降軸43用の開口部211と昇降機構44との間に設けられている。支持板42の形状は、載置台3の支持部材31と干渉せずに昇降できる形状であってもよい。昇降ピン41は、昇降機構44によって、載置台3の表面の上方の側と、載置台3の表面の下方の側との間で、昇降自在に構成される。言い換えると、昇降ピン41は、載置台3の上面から突出可能に構成される。
The elevating mechanism 44 is installed, for example, at the lower part of the exhaust chamber 21. The bellows 45 is provided between the opening 211 for the elevating shaft 43 formed on the lower surface of the exhaust chamber 21 and the elevating mechanism 44. The shape of the support plate 42 may be a shape that can be raised and lowered without interfering with the support member 31 of the mounting table 3. The elevating pin 41 is vertically configured by the elevating mechanism 44 between the upper side of the surface of the mounting table 3 and the lower side of the surface of the mounting table 3. In other words, the elevating pin 41 is configured to be able to project from the upper surface of the mounting table 3.
処理容器2の天壁27には、絶縁部材28を介してガス供給部5が設けられている。ガス供給部5は、上部電極を成しており、下部電極33に対向している。ガス供給部5には、整合器511を介してRF電源51が接続されている。RF電源51の周波数は、例えば、450kHz~2.45GHzである。RF電源51から上部電極(ガス供給部5)にRF電力を供給することによって、上部電極(ガス供給部5)と下部電極33との間にRF電界が生じるように構成されている。ガス供給部5は、中空状のガス拡散室52を備える。ガス拡散室52の下面には、処理容器2内へ処理ガスを分散供給するための多数の孔53が例えば均等に配置されている。ガス供給部5における例えばガス拡散室52の上方には、加熱機構54が埋設されている。加熱機構54は、制御部9からの制御信号に基づいて図示しない電源部から給電されることによって、設定温度に加熱される。
The top wall 27 of the processing container 2 is provided with a gas supply unit 5 via an insulating member 28. The gas supply unit 5 forms an upper electrode and faces the lower electrode 33. An RF power supply 51 is connected to the gas supply unit 5 via a matching unit 511. The frequency of the RF power supply 51 is, for example, 450 kHz to 2.45 GHz. By supplying RF power from the RF power supply 51 to the upper electrode (gas supply unit 5), an RF electric field is generated between the upper electrode (gas supply unit 5) and the lower electrode 33. The gas supply unit 5 includes a hollow gas diffusion chamber 52. On the lower surface of the gas diffusion chamber 52, for example, a large number of holes 53 for dispersing and supplying the processing gas into the processing container 2 are evenly arranged. A heating mechanism 54 is embedded above, for example, the gas diffusion chamber 52 in the gas supply unit 5. The heating mechanism 54 is heated to a set temperature by supplying power from a power supply unit (not shown) based on a control signal from the control unit 9.
ガス拡散室52には、ガス供給路6が設けられている。ガス供給路6は、ガス拡散室52に連通している。ガス供給路6の上流側には、ガスライン62を介してガス源61が接続されている。ガス源61は、例えば各種の処理ガスの供給源、マスフローコントローラ、バルブ(いずれも図示せず)を含む。各種の処理ガスは、前述のシリコン窒化膜の形成方法において用いられる前駆体ガス及び還元性ガスを含む。また、各種の処理ガスは、モノシランガス、ジシランガス等の添加ガスを含んでいてもよい。各種の処理ガスは、ガス源61からガスライン62を介してガス拡散室52に導入される。
The gas diffusion chamber 52 is provided with a gas supply path 6. The gas supply path 6 communicates with the gas diffusion chamber 52. A gas source 61 is connected to the upstream side of the gas supply path 6 via a gas line 62. The gas source 61 includes, for example, various processing gas supply sources, a mass flow controller, and valves (none of which are shown). The various treatment gases include a precursor gas and a reducing gas used in the above-mentioned method for forming a silicon nitride film. Further, the various treatment gases may contain an additive gas such as a monosilane gas or a disilane gas. Various treated gases are introduced from the gas source 61 into the gas diffusion chamber 52 via the gas line 62.
処理装置1は、制御部9を備える。制御部9は、例えばコンピュータであり、CPU(Central Processing Unit)、RAM(Random Access Memory)、ROM(Read Only Memory)、補助記憶装置等を備える。CPUは、ROM又は補助記憶装置に格納されたプログラムに基づいて動作し、処理装置1の動作を制御する。制御部9は、処理装置1の内部に設けられていてもよく、外部に設けられていてもよい。制御部9が処理装置1の外部に設けられている場合、制御部9は、有線又は無線等の通信手段によって、処理装置1を制御できる。
The processing device 1 includes a control unit 9. The control unit 9 is, for example, a computer, and includes a CPU (Central Processing Unit), a RAM (RandomAccessMemory), a ROM (ReadOnlyMemory), an auxiliary storage device, and the like. The CPU operates based on a program stored in the ROM or the auxiliary storage device, and controls the operation of the processing device 1. The control unit 9 may be provided inside the processing device 1 or may be provided outside. When the control unit 9 is provided outside the processing device 1, the control unit 9 can control the processing device 1 by a communication means such as wired or wireless.
〔実施例〕
実施例1では、まず、アスペクト比が1より小さい凹部が表面に形成されたウエハWを準備した。続いて、処理装置1において、載置台3にウエハWを載置した状態で、ガス供給部5から処理容器2内に前駆体ガス及び還元性ガスを含む処理ガスを供給すると共に、RF電源51から上部電極にRF電力を供給し、ウエハWに流動性膜を形成した。続いて、流動性膜が形成されたウエハWを、真空雰囲気下で別の処理装置1に搬送した。続いて、該処理装置1において、N2ガス雰囲気の処理容器2内の載置台3にウエハWを載置した状態で、ウエハWに対して450℃で熱処理を施し、流動性膜を硬化させてシリコン窒化膜を形成した。ウエハWに対する熱処理は、ウエハWへの流動性膜の形成が終了してから1分(60秒)後に開始した。続いて、凹部に埋め込まれたシリコン窒化膜の埋め込み性を、走査型電子顕微鏡(SEM:Scanning Electron Microscope)により観察した。 〔Example〕
In Example 1, first, a wafer W having a concave portion having an aspect ratio smaller than 1 formed on the surface was prepared. Subsequently, in theprocessing apparatus 1, with the wafer W mounted on the mounting table 3, the processing gas containing the precursor gas and the reducing gas is supplied from the gas supply unit 5 into the processing container 2, and the RF power source 51 is used. RF power was supplied from the upper electrode to the wafer W to form a fluid film. Subsequently, the wafer W on which the fluidized film was formed was conveyed to another processing apparatus 1 in a vacuum atmosphere. Subsequently, in the processing apparatus 1, the wafer W is heat-treated at 450 ° C. in a state where the wafer W is placed on the mounting table 3 in the processing container 2 having an N2 gas atmosphere to cure the fluid film. A silicon nitride film was formed. The heat treatment on the wafer W was started 1 minute (60 seconds) after the formation of the fluid film on the wafer W was completed. Subsequently, the embedding property of the silicon nitride film embedded in the recess was observed with a scanning electron microscope (SEM).
実施例1では、まず、アスペクト比が1より小さい凹部が表面に形成されたウエハWを準備した。続いて、処理装置1において、載置台3にウエハWを載置した状態で、ガス供給部5から処理容器2内に前駆体ガス及び還元性ガスを含む処理ガスを供給すると共に、RF電源51から上部電極にRF電力を供給し、ウエハWに流動性膜を形成した。続いて、流動性膜が形成されたウエハWを、真空雰囲気下で別の処理装置1に搬送した。続いて、該処理装置1において、N2ガス雰囲気の処理容器2内の載置台3にウエハWを載置した状態で、ウエハWに対して450℃で熱処理を施し、流動性膜を硬化させてシリコン窒化膜を形成した。ウエハWに対する熱処理は、ウエハWへの流動性膜の形成が終了してから1分(60秒)後に開始した。続いて、凹部に埋め込まれたシリコン窒化膜の埋め込み性を、走査型電子顕微鏡(SEM:Scanning Electron Microscope)により観察した。 〔Example〕
In Example 1, first, a wafer W having a concave portion having an aspect ratio smaller than 1 formed on the surface was prepared. Subsequently, in the
実施例1における流動性膜の成膜条件は以下である。
・前駆体ガス:BTBAS(50sccm)
・還元性ガス:NH3(50sccm)
・添加ガス:H2(50sccm)、He(50sccm)
・圧力:4Torr(533Pa)
・RF電力:13.56MHz、100W
・ウエハ温度:0℃ The film forming conditions of the fluid film in Example 1 are as follows.
-Precursor gas: BTBAS (50 sccm)
-Reducing gas: NH 3 (50 sccm)
-Additional gas: H 2 (50 sccm), He (50 sccm)
-Pressure: 4Torr (533Pa)
・ RF power: 13.56MHz, 100W
・ Wafer temperature: 0 ° C
・前駆体ガス:BTBAS(50sccm)
・還元性ガス:NH3(50sccm)
・添加ガス:H2(50sccm)、He(50sccm)
・圧力:4Torr(533Pa)
・RF電力:13.56MHz、100W
・ウエハ温度:0℃ The film forming conditions of the fluid film in Example 1 are as follows.
-Precursor gas: BTBAS (50 sccm)
-Reducing gas: NH 3 (50 sccm)
-Additional gas: H 2 (50 sccm), He (50 sccm)
-Pressure: 4Torr (533Pa)
・ RF power: 13.56MHz, 100W
・ Wafer temperature: 0 ° C
実施例2では、アスペクト比が5より大きい凹部が表面に形成されたウエハWを準備し、実施例1と同じ条件で、ウエハWに流動性膜を形成し、次いで流動性膜を硬化させてシリコン窒化膜を形成した。続いて、凹部に埋め込まれたシリコン窒化膜の埋め込み性を、SEMにより観察した。
In Example 2, a wafer W having a concave portion having an aspect ratio larger than 5 formed on the surface is prepared, a fluid film is formed on the wafer W under the same conditions as in Example 1, and then the fluid film is cured. A silicon nitride film was formed. Subsequently, the embedding property of the silicon nitride film embedded in the recess was observed by SEM.
比較例1では、ウエハWへの流動性膜の形成が終了してから該流動性膜に対して熱処理を開始するまでの時間を1時間に設定し、それ以外の条件が実施例1と同じ条件で、ウエハWに流動性膜を形成し、次いで流動性膜を硬化させてシリコン窒化膜を形成した。続いて、凹部に埋め込まれたシリコン窒化膜の埋め込み性を、SEMにより観察した。なお、比較例1では、アスペクト比が5より大きい凹部が表面に形成されたウエハWを用いた。
In Comparative Example 1, the time from the completion of the formation of the fluidized film on the wafer W to the start of the heat treatment for the fluidized film is set to 1 hour, and other conditions are the same as in Example 1. Under the conditions, a fluidized film was formed on the wafer W, and then the fluidized film was cured to form a silicon nitride film. Subsequently, the embedding property of the silicon nitride film embedded in the recess was observed by SEM. In Comparative Example 1, a wafer W having a recess formed on the surface having an aspect ratio larger than 5 was used.
比較例2では、前駆体ガスとしてテトラキスジメチルアミノシラン(TeDMAS)を使用し、それ以外の条件が実施例1と同じ条件で、ウエハWに流動性膜を形成し、次いで流動性膜を硬化させてシリコン窒化膜を形成した。続いて、凹部に埋め込まれたシリコン窒化膜の埋め込み性を、SEMにより観察した。なお、比較例2では、アスペクト比が1より小さい凹部が表面に形成されたウエハWを用いた。また、TeDMASは、以下の構造式で示されるように、Si-H結合を有していない対称構造のアミノシラン分子である。
In Comparative Example 2, tetrakisdimethylaminosilane (TeDMAS) was used as the precursor gas, and under the same conditions as in Example 1, a fluid film was formed on the wafer W, and then the fluid film was cured. A silicon nitride film was formed. Subsequently, the embedding property of the silicon nitride film embedded in the recess was observed by SEM. In Comparative Example 2, a wafer W having a recess formed on the surface having an aspect ratio smaller than 1 was used. Further, TeDMAS is an aminosilane molecule having a symmetrical structure having no Si—H bond, as shown by the following structural formula.
図6は、凹部に埋め込まれたシリコン窒化膜の埋め込み性を観察した結果を示す図であり、凹部に埋め込まれたシリコン窒化膜の断面形状を示す。なお、図6では、左から順に実施例1、実施例2、比較例1及び比較例2の結果を示す。
FIG. 6 is a diagram showing the results of observing the embedding property of the silicon nitride film embedded in the recess, and shows the cross-sectional shape of the silicon nitride film embedded in the recess. Note that FIG. 6 shows the results of Example 1, Example 2, Comparative Example 1 and Comparative Example 2 in order from the left.
図6に示されるように、実施例1、2では、いずれも凹部の底部付近にボイド(隙間)やシーム(継ぎ目)のない無孔質で緻密なシリコン窒化膜101が埋め込まれていることが分かる。これは、実施例1、2では、凹部に形成された流動性膜が流動性を維持した状態で熱処理され、該熱処理の際に流動性膜が縮合反応で固化してシリコン窒化膜が形成されたためと考えられる。
As shown in FIG. 6, in Examples 1 and 2, a non-porous and dense silicon nitride film 101 having no voids (gap) or seams (seam) is embedded in the vicinity of the bottom of the recess. I understand. In Examples 1 and 2, the fluid film formed in the recess is heat-treated in a state where the fluidity is maintained, and during the heat treatment, the fluid film is solidified by a condensation reaction to form a silicon nitride film. It is thought that it was a heat treatment.
一方、比較例1では、凹部の底部付近に多数の空孔102aを含む多孔質なシリコン窒化膜102が埋め込まれていることが分かる。これは、比較例1では、凹部に形成された流動性膜が流動性を失った状態で熱処理され、該熱処理の際に膜堆積が低下して多孔質構造となったためと考えられる。
On the other hand, in Comparative Example 1, it can be seen that the porous silicon nitride film 102 including a large number of pores 102a is embedded in the vicinity of the bottom of the recess. It is considered that this is because, in Comparative Example 1, the fluid film formed in the recess was heat-treated in a state where the fluidity was lost, and the film deposition was reduced during the heat treatment to form a porous structure.
また、比較例2では、凹部にシリコン窒化膜が埋め込まれていないことが分かる。これは、比較例2では、前駆体ガスとしてSi-H結合を有していない対称構造のアミノシラン分子を用いたことにより、熱処理を施した後においても凹部に形成された流動性膜の縮合反応による固化が進行せず、流動性膜が消失したためと考えられる。
Further, in Comparative Example 2, it can be seen that the silicon nitride film is not embedded in the recess. This is because in Comparative Example 2, by using an aminosilane molecule having a symmetrical structure that does not have a Si—H bond as the precursor gas, the condensation reaction of the fluid film formed in the recesses even after the heat treatment was performed. It is probable that the solidification did not proceed and the fluid membrane disappeared.
以上の実施例の結果から、実施形態のシリコン窒化膜の形成方法によれば、凹部のアスペクト比に関わらず、緻密なシリコン窒化膜を凹部に埋め込むことができることが示された。
From the results of the above examples, it was shown that according to the method for forming a silicon nitride film of the embodiment, a dense silicon nitride film can be embedded in the recess regardless of the aspect ratio of the recess.
今回開示された実施形態はすべての点で例示であって制限的なものではないと考えられるべきである。上記の実施形態は、添付の請求の範囲及びその趣旨を逸脱することなく、様々な形態で省略、置換、変更されてもよい。
The embodiments disclosed this time should be considered to be exemplary in all respects and not restrictive. The above embodiments may be omitted, replaced or modified in various forms without departing from the scope of the appended claims and their gist.
上記の実施形態では、前駆体ガスとしてSiHx(NCnHm)y(n、m、x、yは1以上の自然数である。)構造の線形非対称アミノシラン分子を用いてシリコン窒化膜を形成する場合を説明したが、本開示はこれに限定されない。例えば、前駆体ガスとしてSiの代わりに金属元素を含む、MHx(NCnHm)y(Mは金属元素であり、n、m、x、yは1以上の自然数である。)構造の線形非対称有機金属分子を用いて金属窒化物膜を形成する場合にも適用できる。すなわち、前駆体ガスとしてXHx(NCnHm)y(XはSi又は金属元素であり、n、m、x、yは1以上の自然数である。)構造の線形非対称有機分子を用いて窒素含有膜を形成する場合に適用できる。なお、金属元素としては、例えばチタン(Ti)、タンタル(Ta)、ジルコニウム(Zr)、アルミニウム(Al)が挙げられる。
In the above embodiment, a silicon nitride film is formed by using a linear asymmetric aminosilane molecule having a SiH x (NC n Hm) y (n, m , x, y are natural numbers of 1 or more) structure as a precursor gas. However, the present disclosure is not limited to this. For example, an MH x (NC n Hm) y ( M is a metal element, and n, m, x, y are natural numbers of 1 or more) containing a metal element instead of Si as a precursor gas. It can also be applied when forming a metal nitride film using linear asymmetric organic metal molecules. That is, using a linear asymmetric organic molecule having an XH x (NC n Hm) y (X is Si or a metal element, and n, m , x, y are natural numbers of 1 or more) as a precursor gas. It can be applied when forming a nitrogen-containing film. Examples of the metal element include titanium (Ti), tantalum (Ta), zirconium (Zr), and aluminum (Al).
上記の実施形態では、処理ガスが前駆体ガス及び還元性ガスを含み、前駆体ガスが線形非対称アミノシラン分子の場合を説明したが、本開示はこれに限定されない。Siを取り巻く結合が非対称であり双極子モーメントが大きくなる構造をもつ線形非対称有機Si分子を使用してよい。例えばSiHx(CnHm)y(n、m、x、yは1以上の自然数である。)構造の非対称有機Si分子を用いる流動性炭素含有絶縁膜としてSiC膜の形成が挙げられる。また、例えば前駆体ガスとして、MHx(CnHm)y(Mは金属元素であり、n、m、x、yは1以上の自然数である。)構造の非対称有機金属分子を用いて金属炭化物膜を形成する場合にも適用できる。すなわち、前駆体ガスとしてXHx(NzCnHm)y(XはSi又は金属元素であり、n、m、x、yは1以上の自然数であり、zは0または1である。)構造の線形非対称有機分子を用いて窒素及び/又は炭素を含有する絶縁膜を形成する場合に適用できる。
In the above embodiment, the case where the treatment gas contains a precursor gas and a reducing gas and the precursor gas is a linear asymmetric aminosilane molecule has been described, but the present disclosure is not limited thereto. A linear asymmetric organic Si molecule having a structure in which the bond surrounding Si is asymmetric and the dipole moment is large may be used. For example, the formation of a SiC film can be mentioned as a fluid carbon-containing insulating film using an asymmetric organic Si molecule having a SiH x (C nH m ) y ( n , m, x, y are natural numbers of 1 or more). Further, for example, as a precursor gas, an asymmetric organic metal molecule having an MH x (C n H m ) y (M is a metal element, and n, m, x, y are natural numbers of 1 or more) is used. It can also be applied when forming a metal carbide film. That is, as the precursor gas, XH x (N z C n H m ) y (X is Si or a metal element, n, m, x, y are natural numbers of 1 or more, and z is 0 or 1. ) Applicable when forming an insulating film containing nitrogen and / or carbon using linear asymmetric organic molecules of structure.
上記の実施形態では、流動性膜を形成する工程と流動性膜を硬化させる工程とを真空搬送装置に接続された異なる処理装置において実施する場合を説明したが、本開示はこれに限定されない。例えば、流動性膜を形成する工程と流動性膜を硬化させる工程とを同じ処理装置において実施してもよい。また例えば、基板を第1の温度に加熱して処理する第1の領域と、基板を第2の温度に加熱して処理する第2の領域とを内部に有する処理装置を用いてもよい。この場合、流動性膜を形成する工程と流動性膜を硬化させる工程とを1つの処理装置内の異なる領域で実施できるので、流動性膜を形成する工程が終了してから流動性膜を硬化させる工程を開始させるまでの移行時間を短縮できる。また、流動性膜が形成された基板を処理装置の外部に搬出することなく流動性膜を硬化させる工程に移行できるので、不純物の混入を特に抑制できる。
In the above embodiment, the case where the step of forming the fluid film and the step of curing the fluid film are carried out in different processing devices connected to the vacuum transfer device has been described, but the present disclosure is not limited to this. For example, the step of forming the fluid film and the step of curing the fluid film may be carried out in the same processing apparatus. Further, for example, a processing apparatus having a first region for heating the substrate to the first temperature for processing and a second region for heating the substrate to the second temperature for processing may be used. In this case, since the step of forming the fluid film and the step of curing the fluid film can be performed in different regions in one processing apparatus, the fluid film is cured after the step of forming the fluid film is completed. It is possible to shorten the transition time until the process of starting the process is started. Further, since the process of curing the fluid film can be performed without carrying the substrate on which the fluid film is formed to the outside of the processing apparatus, it is possible to particularly suppress the mixing of impurities.
本国際出願は、2020年12月22日に出願した日本国特許出願第2020-212899号に基づく優先権を主張するものであり、当該出願の全内容を本国際出願に援用する。
This international application claims priority based on Japanese Patent Application No. 2020-212899 filed on December 22, 2020, and the entire contents of this application will be incorporated into this international application.
1 処理装置
W ウエハ 1 Processing equipment W wafer
W ウエハ 1 Processing equipment W wafer
Claims (13)
- 基板の表面に形成された凹部に窒素及び/又は炭素を含有する絶縁膜を形成する方法であって、
(a)第1の温度に調整された基板に前駆体ガス及び還元性ガスを含む処理ガスをプラズマで活性化して供給することにより前記凹部に流動性膜を形成する工程と、
(b)前記基板を前記第1の温度より高い第2の温度で熱処理することにより前記流動性膜を硬化させる工程と、
を有し、
前記前駆体ガスは、XHx(NzCnHm)y(XはSi又は金属元素であり、n、m、x、yは1以上の自然数であり、zは0または1である。)構造の線形非対称有機分子である、
窒素及び/又は炭素を含有する絶縁膜の形成方法。 A method of forming an insulating film containing nitrogen and / or carbon in a recess formed on the surface of a substrate.
(A) A step of forming a fluid film in the recess by activating and supplying a processing gas containing a precursor gas and a reducing gas to the substrate adjusted to the first temperature by plasma.
(B) A step of curing the fluid film by heat-treating the substrate at a second temperature higher than the first temperature.
Have,
The precursor gas is XH x (N z C n H m ) y (X is Si or a metal element, n, m, x, y are natural numbers of 1 or more, and z is 0 or 1. ) A linear asymmetric organic molecule of structure,
A method for forming an insulating film containing nitrogen and / or carbon. - 前記工程(a)及び前記工程(b)は、真空雰囲気下で連続して実施される、
請求項1に記載の窒素及び/又は炭素を含有する絶縁膜の形成方法。 The step (a) and the step (b) are continuously carried out in a vacuum atmosphere.
The method for forming an insulating film containing nitrogen and / or carbon according to claim 1. - 前記前駆体ガスは、SiHx(NzCnHm)y(n、m、x、yは1以上の自然数であり、zは0または1である。)構造の線形非対称アミノシラン分子である、
請求項1又は2に記載の窒素及び/又は炭素を含有する絶縁膜の形成方法。 The precursor gas is a linear asymmetric aminosilane molecule having a SiH x (N z C n H m ) y (n, m, x, y are natural numbers of 1 or more and z is 0 or 1). ,
The method for forming an insulating film containing nitrogen and / or carbon according to claim 1 or 2. - 前記前駆体ガスは、BTBAS、BDEAS、3DMAS又はBEMASである、
請求項1乃至3のいずれか一項に記載の窒素及び/又は炭素を含有する絶縁膜の形成方法。 The precursor gas is BTBAS, BDEAS, 3DMAS or BEMAS.
The method for forming an insulating film containing nitrogen and / or carbon according to any one of claims 1 to 3. - 前記前駆体ガスは、MHx(NzCnHm)y(MはTi、Ta、Zr又はAlであり、n、m、x、yは1以上の自然数であり、zは0または1である。)構造の線形非対称有機金属分子である、
請求項1又は2に記載の窒素及び/又は炭素を含有する絶縁膜の形成方法。 The precursor gas is MH x (N z C n H m ) y (M is Ti, Ta, Zr or Al, n, m, x, y is a natural number of 1 or more, and z is 0 or 1). It is a linear asymmetric organic metal molecule of structure,
The method for forming an insulating film containing nitrogen and / or carbon according to claim 1 or 2. - 前記還元性ガスは、水素及び/又は窒素を含むガスである、
請求項1乃至5のいずれか一項に記載の窒素及び/又は炭素を含有する絶縁膜の形成方法。 The reducing gas is a gas containing hydrogen and / or nitrogen.
The method for forming an insulating film containing nitrogen and / or carbon according to any one of claims 1 to 5. - 前記第1の温度は、80℃以下であり、
前記第2の温度は、150℃以上750℃以下である、
請求項1乃至6のいずれか一項に記載の窒素及び/又は炭素を含有する絶縁膜の形成方法。 The first temperature is 80 ° C. or lower, and the temperature is 80 ° C. or lower.
The second temperature is 150 ° C. or higher and 750 ° C. or lower.
The method for forming an insulating film containing nitrogen and / or carbon according to any one of claims 1 to 6. - 前記処理ガスは、SiH4ガス及びSi2H6ガスの少なくともいずれかを含む、
請求項1乃至7のいずれか一項に記載の窒素及び/又は炭素を含有する絶縁膜の形成方法。 The processing gas comprises at least one of SiH 4 gas and Si 2 H 6 gas.
The method for forming an insulating film containing nitrogen and / or carbon according to any one of claims 1 to 7. - 前記工程(b)において、前記基板を水素プラズマに晒す、
請求項1乃至8のいずれか一項に記載の窒素及び/又は炭素を含有する絶縁膜の形成方法。 In the step (b), the substrate is exposed to hydrogen plasma.
The method for forming an insulating film containing nitrogen and / or carbon according to any one of claims 1 to 8. - 前記工程(b)は、前記工程(a)の後、60秒以内に行われる、
請求項1乃至9のいずれか一項に記載の窒素及び/又は炭素を含有する絶縁膜の形成方法。 The step (b) is performed within 60 seconds after the step (a).
The method for forming an insulating film containing nitrogen and / or carbon according to any one of claims 1 to 9. - 前記工程(a)と前記工程(b)とを繰返すことを含む、
請求項1乃至10のいずれか一項に記載の窒素及び/又は炭素を含有する絶縁膜の形成方法。 Including repeating the step (a) and the step (b).
The method for forming an insulating film containing nitrogen and / or carbon according to any one of claims 1 to 10. - 基板の表面に形成された凹部に窒素及び/又は炭素を含有する絶縁膜を形成する方法であって、
(a)第1の温度に調整された基板に前駆体ガス及び還元性ガスを含む処理ガスをプラズマで活性化して供給することにより前記凹部に流動性膜を形成する工程と、
(b)前記基板を前記第1の温度より高い第2の温度で熱処理することにより前記流動性膜を硬化させる工程と、
を有し、
前記前駆体ガスは、複数のXHx(NzCnHm)y(XはSi又は金属元素であり、n、m、x、yは1以上の自然数であり、zは0または1である。)構造の線形非対称有機分子の組み合わせである、
窒素及び/又は炭素を含有する絶縁膜の形成方法。 A method of forming an insulating film containing nitrogen and / or carbon in a recess formed on the surface of a substrate.
(A) A step of forming a fluid film in the recess by activating and supplying a processing gas containing a precursor gas and a reducing gas to the substrate adjusted to the first temperature by plasma.
(B) A step of curing the fluid film by heat-treating the substrate at a second temperature higher than the first temperature.
Have,
The precursor gas is a plurality of XH x (N z C n H m ) y (X is Si or a metal element, n, m, x, y are natural numbers of 1 or more, and z is 0 or 1. There is.) A combination of linearly asymmetric organic molecules of structure,
A method for forming an insulating film containing nitrogen and / or carbon. - 凹部が表面に形成された基板を第1の温度に調整し、該基板に前駆体ガス及び還元性ガスを含む処理ガスをプラズマで活性化して供給することにより前記凹部に流動性膜を形成する膜形成部と、
前記基板を前記第1の温度より高い第2の温度で熱処理することにより前記流動性膜を硬化させる熱処理部と、
を備え、
前記前駆体ガスは、XHx(NzCnHm)y(XはSi又は金属元素であり、n、m、x、yは1以上の自然数であり、zは0または1である。)構造の線形非対称有機分子である、
処理装置。 A substrate having a recess formed on the surface is adjusted to a first temperature, and a treatment gas containing a precursor gas and a reducing gas is activated and supplied to the substrate by plasma to form a fluid film in the recess. Membrane forming part and
A heat treatment section that cures the fluid film by heat-treating the substrate at a second temperature higher than the first temperature, and a heat treatment section.
Equipped with
The precursor gas is XH x (N z C n H m ) y (X is Si or a metal element, n, m, x, y are natural numbers of 1 or more, and z is 0 or 1. ) A linear asymmetric organic molecule of structure,
Processing equipment.
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JP2014013905A (en) * | 2007-10-22 | 2014-01-23 | Applied Materials Inc | Methods for forming silicon oxide layer over substrate |
JP2016147861A (en) * | 2015-02-13 | 2016-08-18 | エア プロダクツ アンド ケミカルズ インコーポレイテッドAir Products And Chemicals Incorporated | Bisaminoalkoxysilane compounds and methods for using the same to deposit silicon-containing films |
JP2019534570A (en) * | 2016-11-01 | 2019-11-28 | バーサム マテリアルズ ユーエス,リミティド ライアビリティ カンパニー | Precursor and flowable CVD methods for making low-k films filling surface features |
JP2020516079A (en) * | 2017-04-04 | 2020-05-28 | アプライド マテリアルズ インコーポレイテッドApplied Materials,Incorporated | Two-step process for silicon gap filling |
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JP2014013905A (en) * | 2007-10-22 | 2014-01-23 | Applied Materials Inc | Methods for forming silicon oxide layer over substrate |
JP2016147861A (en) * | 2015-02-13 | 2016-08-18 | エア プロダクツ アンド ケミカルズ インコーポレイテッドAir Products And Chemicals Incorporated | Bisaminoalkoxysilane compounds and methods for using the same to deposit silicon-containing films |
JP2019534570A (en) * | 2016-11-01 | 2019-11-28 | バーサム マテリアルズ ユーエス,リミティド ライアビリティ カンパニー | Precursor and flowable CVD methods for making low-k films filling surface features |
JP2020516079A (en) * | 2017-04-04 | 2020-05-28 | アプライド マテリアルズ インコーポレイテッドApplied Materials,Incorporated | Two-step process for silicon gap filling |
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